CN101180359A - Resin composition - Google Patents
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- CN101180359A CN101180359A CNA2006800177611A CN200680017761A CN101180359A CN 101180359 A CN101180359 A CN 101180359A CN A2006800177611 A CNA2006800177611 A CN A2006800177611A CN 200680017761 A CN200680017761 A CN 200680017761A CN 101180359 A CN101180359 A CN 101180359A
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Abstract
Disclosed is a resin composition wherein birefringence is controlled. Specifically disclosed is a resin composition essentially containing a resin (A) containing a glutarimide unit and an acrylate unit, and another resin (B) containing a glutarimide unit, an acrylate unit and an aromatic vinyl unit. This resin composition can be easily produced at low cost, and is excellent in transparency and heat resistance. In particular, orientational birefringence can be easily controlled in this resin composition. This resin composition can be used for molded bodies for optical applications which require transparency and heat resistance.
Description
Technical field
The present invention relates to resin combination, more specifically, relating to controlled with double refraction is the resin combination of feature.
Background technology
In recent years, electronic equipments is miniaturization day by day, as notebook computer, mobile phone, palm PC representative, and the performance small-sized speciality of light weight and be used for various uses gradually.On the other hand, in the field of flat-panel monitors such as liquid-crystal display, plasma display, also require to suppress picture maximize institute with the weight increase.
In the purposes of the requirement transparency that with aforesaid electronic equipments is representative, the popular gradually parts of glass that will in the past use change to the good resin of the transparency.
Be the various transparent resins of representative with the polymethylmethacrylate because have formability, processibility is good, cracky not, and therefore light weight, cheap feature etc. have carried out using it for the research of liquid-crystal display or CD, pick-up lens etc. and part practicability.
Along with to the expansion with purposes such as parts of head-light for automobile cover, liquid-crystal display, transparent resin not only requires the transparency, also requires thermotolerance.Though polymethylmethacrylate and polystyrene have the feature that the transparency is good, price is also cheaper, because thermotolerance is low, therefore the scope of application is limited in such purposes.
As stable on heating a kind of method of improving polymethylmethacrylate, the method that makes methyl methacrylate and cyclohexyl maleimide amine copolymer is practicability.But, therefore exist and improve thermotolerance, gained interpolymer more with regard to expensive more problem because this method will be used expensive monomer cyclohexyl maleimide one by one.
On the other hand, following scheme has been proposed: in forcing machine, make methoxycarbonyl imidization in the methyl methacrylate by polymethylmethacrylate (patent documentation 1) or copolymer of methyl methacrylatestyrene (patent documentation 2, patent documentation 3, patent documentation 4, patent documentation 5) being handled, thereby obtain the imide series resin with primary amine.The transparency and thermotolerance according to these resins of record are good.Copolymer of methyl methacrylatestyrene particularly, not only can control the reactivity of imidization, and owing to be multipolymer and can control its ratio of components arbitrarily, thereby expect that it has feature widely than the imide series resin that with the polymethylmethacrylate is raw material.But formerly in the technology, the feature of the copolymer of methyl methacrylatestyrene of relevant imidization is clearly record at these.Particularly there is not record about oriented double refraction yet.
Polymkeric substance generally when extrusion moulding etc. polymer chain be orientated, double refraction mostly occurs.In order to eliminate the oriented double refraction of such polymkeric substance, in forming process the 15th volume No. 3 194 pages (non-patent literature 1), proposed to be the monomer that just is being orientated birefringent polymkeric substance and the polymkeric substance that is negative oriented double refraction with suitable proportion carry out random copolymerization method, will have the anisotropic low molecular compound of polarization ratio and be doped in method in the polymkeric substance etc.But, to be the monomer that just is being orientated birefringent polymkeric substance and the polymkeric substance that is negative oriented double refraction carries out random copolymerization with suitable proportion method, combination, the methacrylic acids 2 that use as benzyl methacrylate and methyl methacrylate more, 2, the monomer of the costliness that the combination of 2-trifluoro ethyl ester and methyl methacrylate is such.In addition, will have the anisotropic low molecular compound of polarization ratio and be doped in method in the polymkeric substance, the situation that mostly occurs and from forming composition, spill during the not only price height of low molecular compound, and life-time service, problem is a lot.
In addition, in " Nikkei new materials " September 26 days numbers in 1988 56 pages (non-patent literature 2), as the method for the oriented double refraction that reduces polycarbonate, proposed polycarbonate and polystyrene fusion and make the polystyrene graft copolymerization in the method for polycarbonate etc.But the former lacks the homogeneity on the optical characteristics, and there are problems such as the transparency is low in the intermiscibility of blending resin when low, and in fact the latter exists the operation complicated problems that becomes owing to carrying out graft copolymerization.
Patent documentation 1: No. 4246374, United States Patent (USP)
Patent documentation 2: No. 4727117, United States Patent (USP)
Patent documentation 3: No. 4954574, United States Patent (USP)
Patent documentation 4: No. 5004777, United States Patent (USP)
Patent documentation 5: No. 5264483, United States Patent (USP)
Non-patent literature 1: 194 pages of No. the 3rd, forming process the 15th volumes
Non-patent literature 2:Nikkei new materials, 56 pages of September 26 days numbers in 1988
Summary of the invention
Therefore, need the transparency, excellent heat resistance and can control the resin combination and the manufacture method thereof of oriented double refraction.
The inventor etc. further investigate for solving above-mentioned problem, found that, with the mixed with resin of specific composition and resin combination easy to manufacture, cheap, the transparency and excellent heat resistance, can control oriented double refraction, thereby finished the present invention.
Promptly, the present invention relates to resin (A) and resin (B) is the resin combination of necessary composition, described resin (A) is characterised in that, contain the repeating unit shown in following general formula (1), (2), described resin (B) is characterised in that, contains the repeating unit shown in following general formula (1), (2), (3).
(R
1And R
2The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
3The alkyl of expression hydrogen, carbonatoms 1～18, the cycloalkyl of carbonatoms 3～12 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15.)
(R
4And R
5The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
6The cycloalkyl of alkyl, the carbonatoms 3～12 of expression carbonatoms 1～18 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15.)
(R
7The alkyl of expression hydrogen or carbonatoms 1～8, R
8The aryl of expression carbonatoms 6～10.)
As preferred embodiment, the present invention relates to following resin combination, it is characterized in that, contain resin (A) 0.1～50 weight %, resin (B) 50～99.9 weight %.
As preferred embodiment, the present invention relates to following resin combination, it is characterized in that oriented double refraction is 0～0.1 * 10
-3
As preferred embodiment, the present invention relates to following resin combination, it is characterized in that photoelastic coefficient is 10 * 10
-12m
2Below/the N.
As preferred embodiment, the present invention relates to following resin combination, it is characterized in that second-order transition temperature is more than 110 ℃.
The invention still further relates to the optical resin composition of above-mentioned resin combination as main component.
The invention still further relates to the optical resin forming composition of above-mentioned resin combination as main component.
The invention still further relates to the manufacture method of resin combination: obtain resin combination by hybrid resin (A) and resin (B), described resin (A) obtains after (methyl) acrylic ester polymer (C) is handled with the imidization agent, and described resin (B) obtains after (methyl) acrylate-aromatic vinyl base co-polymer (D) is handled with the imidization agent.
The invention still further relates to: the manufacture method that obtains resin combination after the resin combination that will contain (methyl) acrylic ester polymer (C), (methyl) acrylate-aromatic vinyl base co-polymer (D) is handled with the imidization agent.
That the present invention can provide is easy to manufacture, cheap, the control of the transparency and excellent heat resistance, particularly oriented double refraction is easy to resin combination.Resin combination of the present invention can also be used for the optics forming composition of requirement transparency and heat-proof.
Embodiment
The present invention relates to resin (A) and resin (B) is the resin combination of necessary composition, described resin (A) is characterised in that, contain the repeating unit shown in following general formula (1), (2), described resin (B) is characterised in that, contains the repeating unit shown in following general formula (1), (2), (3).
(R
1And R
2The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
3The alkyl of expression hydrogen, carbonatoms 1～18, the cycloalkyl of carbonatoms 3～12 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15.)
(R
4And R
5The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
6The cycloalkyl of alkyl, the carbonatoms 3～12 of expression carbonatoms 1～18 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15.)
(R
7The alkyl of expression hydrogen or carbonatoms 1～8, R
8The aryl of expression carbonatoms 6～10.)
As the present invention one of must composition with contain the repeating unit shown in general formula (1), (2) be feature resin (A) first to constitute the unit be the unit shown in the general formula (1), generally be called glutarimide unit (following sometimes general formula (1) simply is expressed as the glutarimide unit) more.
As preferred glutarimide unit, R
1, R
2Be hydrogen or methyl, R
3Be hydrogen, methyl or cyclohexyl.Preferred especially R
1Be methyl, R
2Be hydrogen, R
3Be methyl.
This glutarimide unit can be a single kind, also can comprise R
1, R
2, R
3Different a plurality of kinds.
It is the unit shown in the general formula (2) that second of resin (A) constitutes the unit, generally is called (methyl) acrylic ester unit (following sometimes general formula (2) simply is expressed as (methyl) acrylic ester unit) more.
Give that there is no particular restriction with (methyl) acrylic acid series compound of above-mentioned (methyl) acrylic ester unit or (methyl) acrylate based compound, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate etc.In addition, the half ester of the straight or branched alcohol of acid anhydrides such as maleic anhydride or they and carbonatoms 1～20; α such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, Ba Dousuan, fumaric acid, citraconic acid, β-ethene unsaturated carboxylic acid etc. also can imidizations, thereby can be used for the present invention.Wherein, special preferable methyl methyl acrylate.
These second formation unit can be single kind, also can comprise R
4, R
5, R
6Different a plurality of kinds.
As the present invention one of must composition with contain the repeating unit shown in general formula (1), (2), (3) be feature resin (B) first to constitute the unit be the unit shown in the general formula (1), generally be called the glutarimide unit more.
As preferred glutarimide unit, R
1, R
2Be hydrogen or methyl, R
3Be hydrogen, methyl or cyclohexyl.Preferred especially R
1Be methyl, R
2Be hydrogen, R
3Be methyl.
This glutarimide unit can be a single kind, also can comprise R
1, R
2, R
3Different a plurality of kinds.
It is the unit shown in the general formula (2) that second of resin (B) constitutes the unit, generally is called (methyl) acrylic ester unit more.
Give that there is no particular restriction with (methyl) acrylic acid series compound of above-mentioned (methyl) acrylic ester unit or (methyl) acrylate based compound, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate etc.In addition, the half ester of the straight or branched alcohol of acid anhydrides such as maleic anhydride or they and carbonatoms 1～20; α such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, Ba Dousuan, fumaric acid, citraconic acid, β-ethene unsaturated carboxylic acid etc. also can imidizations, thereby can be used for the present invention.Wherein, special preferable methyl methyl acrylate.
These second formation unit can be single kind, also can comprise R
4, R
5, R
6Different a plurality of kinds.
Constituting the unit as the 3rd of resin (B), is the unit shown in the general formula (3), generally is called aromatic ethenyl unit (following sometimes general formula (3) simply is expressed as the aromatic ethenyl unit) more.
Constitute the unit as preferred aromatic ethenyl, can enumerate vinylbenzene, alpha-methyl styrene etc.Wherein, special optimization styrene.
These the 3rd formation unit can be single kind, also can comprise R
7, R
8Different a plurality of kinds.
Resin (A) and the unitary preferred content of glutarimide shown in resin (B) formula of (1) that must composition as the present invention be 20 weight %～95 weight %, 25～90 weight % more preferably, and then preferred 30～80 weight %.If the glutarimide unit is less than this scope, the thermotolerance deficiency of gained imide resin is transparent impaired sometimes.In addition, if surpass this scope, then thermotolerance unnecessarily improves and is difficult to moulding, and the physical strength of gained forming composition extremely becomes fragile and be transparent impaired sometimes in addition.
As the present invention must composition resin (B) formula of (3) shown in the unitary content of aromatic ethenyl, be benchmark with total repetition unit of resin (B), the scope of preferred 1 weight %～80 weight %.Preferred content is 5 weight %～60 weight %.If the aromatic ethenyl unit is greater than this scope, the thermotolerance deficiency of gained imide resin sometimes, if less than this scope, the physical strength of gained forming composition descends sometimes.
As required, can be in resin (A) that must composition as the present invention and resin (B) further copolymerization have other to constitute the unit.Constitute the unit as other, can use nitriles such as vinyl cyanide, methacrylonitriles be monomer, and maleimides such as maleimide, N-methyl maleimide, N-phenylmaleimide, N-cyclohexyl maleimide are monomer copolymerization and the formation unit that forms.They directly copolymerization also can graft copolymerization in resin.
Resin combination of the present invention can also reduce optical anisotropy.Here said optical anisotropy is little not only to require the optical anisotropy of direction (length direction, width) in the face of film little, and the optical anisotropy of going back the required thickness direction is also little.Promptly mean, the direction of specific refractory power maximum in the face is made as X-axis, be made as Y-axis with the vertical direction of X-axis, the thickness direction of film is made as the Z axle, each axial specific refractory power is made as nx, ny, nz, film thickness is made as d, then phase differential Re=(nx-ny) in the face * d and thickness direction phase differential Rth=| (nx+ny)/2-nz| * d (|| expression absolute value) all little (phase differential Re and thickness direction phase differential Rth are 0 in the complete optically isotropic film on the ideal three-dimensional, face).
Resin combination of the present invention is characterised in that, can control oriented double refraction (in addition, as required, can also be adjusted into specific oriented double refraction and use).So-called oriented double refraction is meant the double refraction that presents when stretching under specified temperature, regulation stretching ratio.Unless otherwise specified, just be meant under 100% double refraction that presents when stretching in this specification sheets than the high 5 ℃ temperature of the second-order transition temperature of imide resin.Here, oriented double refraction is defined as Δ n=nx-ny=Re/d with above-mentioned nx, ny, measures by phasometer.
As the value of oriented double refraction, preferred 0～0.1 * 10
-3, more preferably 0～0.01 * 10
-3Oriented double refraction is outside above-mentioned scope the time, easily produces double refraction with the variation of environment when forming process and is difficult to obtain stable optical characteristics.
In order there not to be the resin combination of oriented double refraction basically, in general it is necessary respectively constituting unitary amount in the telomerized polymer, but be difficult to sometimes make oriented double refraction reach above-mentioned scope with available raw material, perhaps thermotolerance of gained resin etc. is limited.
For oriented double refraction being adjusted to above-mentioned scope, repeating unit shown in repeating unit shown in the general formula (1) and the general formula (3) is in weight ratio, preferably 2.0: 1.0～4.0: 1.0 scope, more preferably 2.5: 1.0～4.0: 1.0 scope, and then preferred 3.0: 1.0～3.5: 1.0 scope.In addition, when replacing weight ratio to carry out regulation with mol ratio, repeating unit shown in repeating unit shown in the general formula (1) and the general formula (3) is with molar ratio computing, preferably 1.0: 1.0～4.0: 1.0 scope, more preferably 1.0: 1.0～3.0: 1.0 scope, and then preferred 1.2: 1.0～2.5: 1.0 scope.What should illustrate is that above-mentioned mol ratio is meant the ratio of each number of repeat unit that comprises in the multipolymer.
As the resin (A) of resin combination of the present invention and resin (B) blending ratio preferably, preferred resin (A) 0.1～50 weight %, resin (B) 50～99.9 weight %.By in this scope, changing the blending ratio of resin, can be at the good scope control oriented double refraction of thermotolerance.And then, respectively constitute unitary amount by what regulate resin (A) and resin (B), can control oriented double refraction in wideer scope.
In addition, the unitary content of aromatic ethenyl shown in the general formula that comprises in the resin combination of the present invention (3), preferred 1～70 weight %.If the aromatic ethenyl unit is greater than this scope, the thermotolerance deficiency of gained imide resin sometimes, if less than this scope, the physical strength of gained forming composition descends sometimes.
The present invention removes the resin combination beyond the region of objective existence that modulation does not as mentioned above have oriented double refraction basically, in that modulation has on the resin combination this point of required oriented double refraction according to purposes, also is useful.
Resin combination of the present invention preferably has 1 * 10
4～5 * 10
5Weight-average molecular weight.Weight-average molecular weight when above-mentioned value is following, the physical strength deficiency during film forming, when above-mentioned value is above, the viscosity height during fusion, the productivity of film descends.
The second-order transition temperature of resin combination is preferably more than 110 ℃, more preferably more than 120 ℃, so that preferred more than 125 ℃.Second-order transition temperature when above-mentioned value is following, the thermotolerance deficiency of resin, thereby purposes is limited.
Can add other thermoplastic resin as required in the resin combination of the present invention.
The photoelastic coefficient of resin combination of the present invention is preferably 10 * 10
-12m
2Below/the N, more preferably 5 * 10
-12m
2Below/the N.The absolute value of photoelastic coefficient is greater than 10 * 10
-12m
2During/N, easily cause light leak, particularly this tendency becomes remarkable under the environment of hot and humid degree.
So-called photoelastic coefficient when producing stress (Δ F) when isotropic solid is applied external force, temporarily presents optical anisotropy, thereby shows double refraction (Δ n), and this stress and birefringent ratio are called photoelastic coefficient (c), represents with following formula.
c＝Δn/ΔF
In the present invention, photoelastic coefficient is to measure the value that obtains according to Sai Nameng (Senarmont) method, with wavelength 515nm, under 23 ℃, 50%RH.
Composition of the present invention obtains by hybrid resin (A) and resin (B), described resin (A) obtains after (methyl) acrylic ester polymer (C) is handled with the imidization agent, and described resin (B) obtains after (methyl) acrylate-aromatic vinyl base co-polymer (D) is handled with the imidization agent.
Composition of the present invention can also be handled with imidization by the resin combination that will contain (methyl) acrylic ester polymer (C), (methyl) acrylate-aromatic vinyl base co-polymer (D) and obtain.
Resin (A) that one of must composition as the present invention for example can obtain by (methyl) acrylic ester polymer (C) is carried out imidization.
As operable among the present invention (methyl) acrylic ester polymer (C), so long as with in following five kinds of compounds any one as getting final product by composition, can be wire (linear) polymkeric substance, can also be block polymer, core-shell polymer, branched polymer, ladder polymer, cross-linked polymer; Described five kinds of compounds are that (1) is polymer of monomers can carry out imidization reaction (methyl) acrylic acid series compound, (2) be polymer of monomers with (methyl) acrylate based compound that can carry out imidization reaction, (3) be monomeric multipolymer with (methyl) acrylic acid series compound and (methyl) acrylate based compound, (4) (methyl) acrylic acid series compound or (5) (methyl) acrylate based compound.Block polymer can be the block polymer of A-B type, A-B-C type, A-B-A type or any type in addition.Core-shell polymer can only contain one deck nuclear and one deck shell, also can examine and each self-forming multilayer of shell.
Wherein, from acquired, rerum natura, reactive balance, preferable methyl methyl acrylate based polymer it is desirable to the linear copolymers of type homopolymer, methyl methacrylate and the alkyl acrylate of methyl methacrylate especially.
Resin of the present invention (B) for example can obtain by (methyl) acrylate-aromatic vinyl base co-polymer (D) is carried out imidization.
As operable among the present invention (methyl) acrylate-aromatic vinyl base co-polymer (D), so long as with any one and polystyrene compound in following five kinds of compounds as getting final product by composition, can be wire (linear) polymkeric substance, can also be block polymer, core-shell polymer, branched polymer, ladder polymer, cross-linked polymer; Described five kinds of compounds are that (1) is polymer of monomers can carry out imidization reaction (methyl) acrylic acid series compound, (2) be polymer of monomers with (methyl) acrylate based compound that can carry out imidization reaction, (3) be monomeric multipolymer with (methyl) acrylic acid series compound and (methyl) acrylate based compound, (4) (methyl) acrylic acid series compound or (5) (methyl) acrylate based compound.Block polymer can be A-B type, A-B-C type, A-B-A type, or the block polymer of any type in addition.Core-shell polymer can only contain one deck nuclear and one deck shell, also can examine and each self-forming multilayer of shell.
Wherein, from acquired, rerum natura, reactive balance, it is desirable to methyl methacrylate and cinnamic multipolymer especially.
Resin combination of the present invention can be pre-mixed (methyl) acrylic ester polymer (C) and (methyl) acrylate-aromatic vinyl base co-polymer (D), then this resin combination is handled with the imidization agent and is obtained.As blending ratio preferably, preferred (methyl) acrylic ester polymer (C) 0.1～50 weight %, (methyl) acrylate-aromatic vinyl base co-polymer (D) 50～99.9 weight %.By changing the blending ratio of resin in this scope, the good scope inner control oriented double refraction of thermotolerance of resin combination that can be behind imidization.And then, respectively constitute unitary amount by what regulate (methyl) acrylic ester polymer (C) and (methyl) acrylate-aromatic vinyl base co-polymer (D), can control oriented double refraction in wideer scope.
As long as the imidization agent can generate the glutarimide unit shown in the general formula (1) and just be not particularly limited, can enumerate for example ammonia; The amine of fatty family alkyl such as methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine, n-Butyl Amine 99, isobutylamine, TERTIARY BUTYL AMINE, normal hexyl Amine; Aniline, benzylamine, Tolylamine, trichloroaniline etc. contain the amine of aromatic hydrocarbyl; The amine of that include cycloaliphatic hydrocarbons bases such as hexahydroaniline.In addition, can also use urea, 1,3-dimethyl urea, 1,3-diethyl urea, 1,3-dipropyl urea is such passes through the urea based compound that heating generates their amine.In these imidization agent, from cost, rerum natura aspect, preferred methylamine, ammonia, hexahydroaniline, wherein, preferred especially methylamine.
Imidization reaction is preferably carried out the imidization agent and is handled under inert gas environment.If under the condition that oxygen exists, carry out the processing of imidization agent, because therefore the tendency that the visible yellow color degree worsens preferably will fully replace with rare gas elementes such as nitrogen in the system.
The addition of imidization agent depends on the imidization rate that is used to present necessary rerum natura, in order to reduce the yellow chromaticity of gained resin combination, below preferred 40 weight parts, more preferably below 30 weight parts.The addition of used imidization agent is when 40 weight parts are above, because the tendency that the yellow chromaticity of visible resin combination raises, thereby can't obtain water white resin sometimes.
In order to obtain resin combination of the present invention, just be not particularly limited so long as can under inert gas environment, carry out the device of imidization agent processing, for example can use forcing machine etc., also can use batch-type reactive tank (pressurized vessel) etc.
When the manufacturing of resin combination of the present invention is carried out with forcing machine, various forcing machines can be used, for example single shaft forcing machine, biaxial extruder or multiple screw extruder etc. can be used.As promoting imidization agent and stock polymer blended forcing machine, preferred especially biaxial extruder.
Biaxial extruder has that non-occlusal pattern is rotary in the same way, rotary in the same way, the non-occlusal pattern heterodromy of occlusal pattern, occlusal pattern heterodromy etc.; In the biaxial extruder, can high speed rotating because occlusal pattern is rotary in the same way, can promote mixing of imidization agent and stock polymer, thereby be preferred.These forcing machines can use separately, also can be connected in series.
The resin decomposition that imidization is carried out and suppress to be caused by superfluous thermal history, yellow chromaticity etc., temperature of reaction is carried out 150～400 ℃ scope.Preferred 180～320 ℃, and then preferred 200～290 ℃.
In addition, in order to remove by product and/or monomer class such as unreacted imidization agent or primary alconol class in the forcing machine, preferred installation can be decompressed to the following ventilation opening of normal atmosphere.
Can also use the such vertical double-shaft steel basin of the BIVOLAK of the system of Sumitomo heavy-duty machine tool (strain) for example such horizontal-type biaxial reaction unit, SUPERBLEND etc. to replace forcing machine well corresponding to full-bodied reaction unit.
When the manufacture method of resin combination of the present invention uses batch-type reactive tank (pressurized vessel) to carry out, so long as can be under inert gas environment by heating with the material resin fusion, can stir, and the structure that can add the imidization agent just be not particularly limited, sometimes melt viscosity rises owing to the carrying out of reaction, so the good structure of stirring efficiency is good.For example, can enumerate the steel basin MAXBLEND etc. of the system of Sumitomo heavy-duty machine tool (strain) for example.
When carrying out imidization, can in the scope of not damaging the object of the invention, add the general catalyzer that uses, antioxidant, thermo-stabilizer, softening agent, lubricant, UV light absorber, antistatic agent, tinting material, anti-shrinking medium etc. with the imidization agent.
Secondary carboxyl, the anhydride group that generates is purpose when making to reduce, and resin combination of the present invention can also carry out modification with esterifying agent.
As esterifying agent, can enumerate for example methylcarbonate, 2, the 2-Propanal dimethyl acetal, methyl-sulphoxide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, diphenyl carbonate, methyl-sulfate, the toluenesulphonic acids methyl esters, the trifluoromethanesulfonic acid methyl esters, methyl acetate, methyl alcohol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, the dimethyl carbodiimide, dimethyl tertiary butyl chloride silane, methylvinyl acetate, dimethyl urea, tetramethylammonium hydroxide, dimethyldiethoxysilane, four n-butoxy silane, dimethyl (TMS) phosphorous acid ester, trimethyl phosphite, trimethyl phosphite 99, Tritolyl Phosphate, diazomethane, oxyethane, propylene oxide, cyclohexene oxide, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether etc.
The resin combination that obtains among the present invention can use itself, perhaps also can with other resin fusion.
With the resin of resin combination of the present invention as main component, can be used as the optical resin composition well, also can be used as the optical resin forming composition well.
As the forming method of the forming composition that forms by imide resin of the present invention, can use known in the past any means.Can enumerate for example injection molding, melt extrude the film moulding, inflation moulding, blow molding, compressed moulding, spinning moulding etc.In addition, can also be to make imide resin of the present invention be dissolved in the solution casting method that carries out moulding behind its solvent of solubilized.Can adopt any means wherein, but from being easy to significantly to represent effect of the present invention or manufacturing cost, the solvent viewpoints such as influence to global environment, that does not preferably use solvent melt extrudes the film moulding.
During forming process, can in the scope of not damaging the object of the invention, add the general antioxidant that uses, thermo-stabilizer, softening agent, lubricant, UV light absorber, antistatic agent, tinting material, anti-shrinking medium, weighting agent etc.
Embodiment
Further describe the present invention based on embodiment, but the present invention is not limited in these embodiment.In addition, each measuring method of the rerum natura of measuring in following examples and the comparative example is as follows.
(1) mensuration of imidization rate
Former state is used the resultant particle, uses the TravelIR of SensIR Tecnologies corporate system, at room temperature measures IR spectrum.According to the gained spectrogram, by 1720cm
-1Absorption intensity that belongs to ester carbonyl group and 1660cm
-1The imidization rate of recently obtaining of the absorption intensity that belongs to the imide carbonyl.Here, so-called imidization rate is meant imide carbonyl shared ratio in whole carbonyls.
(2) styrene content
10mg is dissolved in CDCl with resultant
31g, the NMR determinator Gemini-300 of use Varian corporate system at room temperature measures
1H-NMR.According to the gained spectrogram, by the recently definite styrene content of the integrated intensity that belongs to aromatic protons with the integrated intensity that belongs to the aliphatics proton.
(3) second-order transition temperature (Tg)
Use resultant 10mg,, under nitrogen environment, measure, determine by mid-point method with 20 ℃/min of heat-up rate with differential scanning calorimeter (DSC, the system DSC-50 of (strain) Shimadzu Seisakusho Ltd. type).
(4) total light transmittance
Resin combination is dissolved in methylene dichloride (resin concentration 25wt%), coats on the PET film, drying is also made film.Cut out the test film of 50mm * 50mm size from this film.Use the turbidometer 300A of Japanese electric look industry system,, measure this test film according to JIS K7105 in 23 ℃ ± 2 ℃ of temperature, humidity 50% ± 5% time.
(5) turbidity
Use the turbidometer 300A of Japanese electric look industry system,, measure the test film that obtains in (4) according to JIS K7136 in 23 ℃ ± 2 ℃ of temperature, humidity 50% ± 5% time.
(6) oriented double refraction
The film of making from (4) cuts out the sample of wide 50mm * long 150mm, with 2 times of stretching ratios, make monadic stretching membrane under the temperature higher 5 ℃ than second-order transition temperature.Cut out the test film of 35mm * 35mm from the central part of this monadic stretching membrane TD direction.Use automatic double refraction meter (the system KOBRA-WR of prince's instrumentation machine Co., Ltd.), in 23 ℃ ± 2 ℃ of temperature, humidity 50% ± 5% time, at wavelength 590nm, 0 ° of phase differential of measuring this test film of input angle.With Digimatic Indicator (Mitutoyo Corporation system) determination test sheet thickness, the value that this phase differential is obtained divided by this thickness is as oriented double refraction.
(Production Example 1)
Use commercially available methacrylic resin (Sumitomo Chemical Company Ltd's system, SumipexMH), make imide resin as the Monomethylamine of imidization agent.Employed forcing machine is the rotary in the same way biaxial extruder of the occlusal pattern of bore 40mm.Under the condition of 270 ℃ of the design temperatures in each temperature adjustment zone of forcing machine, screw rod revolution 200rpm, supply with methacrylic resin with 20kg/hr, the feed rate of Monomethylamine is 25 weight parts with respect to methacrylic resin.Drop into methacrylic resin from hopper, after making the resin fusion by mediating piece (kneading block), being full of, inject Monomethylamine from nozzle.Terminal sealing filler ring at conversion zone is full of resin.Ventilation opening pressure is decompressed to-0.09MPa, makes reacted by product and superfluous methylamine volatilization.After the mouth mould that is arranged at outlet of extruder cools off tank with the thread resin that is extruded, use the tablets press granulating.
Imidization rate, the second-order transition temperature of gained imide resin (a) are recorded in table 1.
[table 1]
| Production Example | Commercially available imide resin | |||
| 1 | 2 | 3 | ||
| Imide resin | (a) | (b) | (c) | (d) |
| Vinylbenzene ratio (mole %) | 0 | 22 | 30 | 0 |
| Imidization rate (mole %) | 69 | 70 | 70 | 70 |
| Second-order transition temperature (℃) | 155 | 157 | 152 | 156 |
(Production Example 2)
With the method same, use copolymer of methyl methacrylatestyrene (St content 22wt%), make imide resin as the Monomethylamine of imidization agent with Production Example 1.Under the condition of 270 ℃ of the design temperatures in each temperature adjustment zone of forcing machine, screw rod revolution 200rpm, supply with polymethylmethacrylate-styrol copolymer with 20kg/hr, the feed rate of Monomethylamine is 20 weight parts with respect to polymethylmethacrylate-styrol copolymer.
Imidization rate, second-order transition temperature, the styrene content of gained imide resin (b) are recorded in table 1.
(Production Example 3)
Except that using copolymer of methyl methacrylatestyrene (St content 30wt%), use with the same method of Production Example 1 and make.
Imidization rate, second-order transition temperature, the styrene content of gained imide resin (c) are recorded in table 1.
(embodiment 1)
The imide resin (b) that obtains in the imide resin (a) that obtains in the Production Example 1 and the Production Example 2 is counted 10/90 mixed with weight ratio, obtain resin combination, total light transmittance, turbidity, the oriented double refraction of the film that is obtained by this resin combination are shown in table 2.
[table 2]
| Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 1 | ||
| Blended ratio | Kind | (a)/(b) | (a)/(c) | (b)/(d) | (b) |
| (weight %/weight %) | 10/90 | 33/67 | 90/10 | 100 | |
| The transparency: turbidity (%) | 0.7 | 0.5 | 0.7 | 0.5 | |
| Total light transmittance | 92 | 92 | 92 | 91 | |
| Oriented double refraction (* 10 -3) | 0.03 | 0.05 | 0.05 | 0.12 | |
(embodiment 2)
The imide resin (c) that obtains in the imide resin (a) that obtains in the Production Example 1 and the Production Example 3 is counted 33/67 mixed with weight ratio, obtain resin combination, total light transmittance, turbidity, the oriented double refraction of the film that is obtained by this resin combination are shown in table 2.
(embodiment 3)
With the imide resin (b) that obtains in the Production Example 2 and commercially available imide resin (d) (Rohm corporate system, PLEXIMID8805, the imidization rate of resin, second-order transition temperature, styrene content are shown in table 1) count 90/10 mixed with weight ratio, obtain resin combination, total light transmittance, turbidity, the oriented double refraction of the film that is obtained by this resin combination are shown in table 2.
(comparative example 1)
Total light transmittance, turbidity, the oriented double refraction of the film that is made by the imide resin that obtains in the Production Example 2 (b) are shown in table 2.
(embodiment 4)
(Sumitomo Chemical Company Ltd's system, SumipexMH) 10 weight % and methyl methacrylate-styrene copolymerized resin (St content 22wt%) 90 weight % do and mix, and obtain resin with commercially available methacrylic resin.Use this resin, with Monomethylamine as imidization agent make imide resin.Employed forcing machine is the rotary in the same way biaxial extruder of the occlusal pattern of bore 40mm.Under the condition of 270 ℃ of the design temperatures in each temperature adjustment zone of forcing machine, screw rod revolution 200rpm, supply with resin combination with 20kg/hr, the feed rate of Monomethylamine is 20 weight parts with respect to methacrylic resin.Drop into resin combination from hopper, after making the resin fusion by mediating piece, being full of, inject Monomethylamine from nozzle.Terminal sealing filler ring at conversion zone is full of resin.The pressure of ventilation opening is decompressed to-0.09MPa, makes reacted by product and superfluous methylamine volatilization.After the mouth mould that is arranged at outlet of extruder cools off tank with the thread resin that is extruded, use the tablets press granulating.
Total light transmittance, turbidity, the oriented double refraction of imidization rate, second-order transition temperature and the film of gained resin combination are recorded in table 3.
[table 3]
| Embodiment | Comparative example | |||
| 4 | 5 | 6 | 2 | |
| Imidization rate (mole %) | 68 | 70 | 69 | 68 |
| Second-order transition temperature (℃) | 155 | 157 | 156 | 156 |
| The transparency: turbidity (%) | 0.7 | 0.5 | 0.7 | 0.5 |
| Total light transmittance | 92 | 92 | 92 | 91 |
| Oriented double refraction (* 10 -3) | 0.02 | 0.04 | 0.05 | 0.12 |
(embodiment 5)
Use commercially available methacrylic resin (Sumitomo Chemical Company Ltd's system, Sumipex MH) 33 weight % and methyl methacrylate-styrene copolymerized resin (St content 30wt%) 67 weight % do the resin that mixes and obtain, in addition, use method similarly to Example 4 to obtain resin combination.
Total light transmittance, turbidity, the oriented double refraction of imidization rate, second-order transition temperature and the film of gained resin combination are recorded in table 3.
(embodiment 6)
Use commercially available methacrylic resin (Sumitomo Chemical Company Ltd's system, Sumipex MH) 50 weight % and methyl methacrylate-styrene copolymerized resin (St content 40wt%) 50 weight % do the resin that mixes and obtain, in addition, use method similarly to Example 4 to obtain resin combination.
Total light transmittance, turbidity, the oriented double refraction of imidization rate, second-order transition temperature and the film of gained resin combination are recorded in table 3.
(comparative example 2)
Except that using methyl methacrylate-styrene copolymerized resin (St content 22wt%), use method similarly to Example 4 to obtain imide resin.
Total light transmittance, turbidity, the oriented double refraction of imidization rate, second-order transition temperature and the film of gained imide resin are recorded in table 3.
Moulding product by resin combination of the present invention obtains can directly be used for various uses as the finished product.Perhaps can carry out being used for various uses after the various processing.Can enumerate image fields such as phtographic lens that photographic camera for example or VTR, projector use or view finder, spectral filter, prism, Fresnel lens; The CD of CD Player or DVD player, MD player etc. is with lens fields such as pick-up lenss; CDs such as CD Player or DVD player, MD player are used the optical recording field; Information instrument field such as liquid crystal liquid-crystal displays such as light guiding plate, polarizer protective membrane or phase retardation film film, surface protection film; Optical communication fields such as optical fiber, photoconverter, optical connector; Automotive fields such as automobile headlamp or taillight lens, interior lens, measuring instrument shell, sunshade; The medical instruments fields such as medical treatment product of glasses or contact lens, endoscope-use lens, essential sterilising treatment; Road light-passing board, double glazing with lens, light inlet window or bicycle shed, illumination with camera lens or illumination cover, building materials with building materials fields such as sizing materials; Micro-wave cooking container (tableware) etc.Forming composition particularly of the present invention and film; utilize its excellent optics uniformity, the transparency, low-birefringence etc., can perform well in known optical purposes such as liquid crystal indicator periphery such as optical isotropy film, polarizer protective membrane or nesa coating.
Claims (9)
1. resin combination, as must composition, described resin (A) be characterised in that, contains the repeating unit shown in following general formula (1), (2) with resin (A) and resin (B) for it, described resin (B) is characterised in that, contains the repeating unit shown in following general formula (1), (2), (3);
Wherein, R
1And R
2The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
3The alkyl of expression hydrogen, carbonatoms 1～18, the cycloalkyl of carbonatoms 3～12 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15;
Wherein, R
4And R
5The alkyl of representing hydrogen or carbonatoms 1～8 independently of one another, R
6The cycloalkyl of alkyl, the carbonatoms 3～12 of expression carbonatoms 1～18 or contain the substituting group of aromatic nucleus, wherein, the carbonatoms of described aromatic nucleus is 5～15;
Wherein, R
7The alkyl of expression hydrogen or carbonatoms 1～8, R
8The aryl of expression carbonatoms 6～10.
2. resin combination according to claim 1 is characterized in that, contains resin (A) 0.1～50 weight %, resin (B) 50～99.9 weight %.
3. resin combination according to claim 1 and 2 is characterized in that, oriented double refraction is 0～0.1 * 10
-3
4. according to each described resin combination in the claim 1～3, it is characterized in that photoelastic coefficient is 10 * 10
-12m
2Below/the N.
5. according to each described resin combination in the claim 1～4, it is characterized in that second-order transition temperature is more than 110 ℃.
6. an optical resin composition is characterized in that, with each described resin combination in the claim 1～5 as main component.
7. an optical resin forming composition is characterized in that, with the described resin combination of claim 6 as main component.
8. the manufacture method of each described resin combination in the claim 1～5, it is characterized in that, obtain resin combination by hybrid resin (A) and resin (B), described resin (A) obtains after (methyl) acrylic ester polymer (C) is handled with the imidization agent, and described resin (B) obtains after (methyl) acrylate-aromatic vinyl base co-polymer (D) is handled with the imidization agent.
9. the manufacture method of each described resin combination in the claim 1～5, it is characterized in that the resin combination that will contain (methyl) acrylic ester polymer (C), (methyl) acrylate-aromatic vinyl base co-polymer (D) obtains each described resin combination in the claim 1～5 after handling with the imidization agent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP158201/2005 | 2005-05-30 | ||
| JP2005158201 | 2005-05-30 | ||
| JP158206/2005 | 2005-05-30 |
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| Publication Number | Publication Date |
|---|---|
| CN101180359A true CN101180359A (en) | 2008-05-14 |
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ID=39406011
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800177611A Pending CN101180359A (en) | 2005-05-30 | 2006-05-26 | Resin composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103380175A (en) * | 2011-02-21 | 2013-10-30 | 株式会社钟化 | Acrylic resin film |
| CN103619946A (en) * | 2011-07-01 | 2014-03-05 | 旭化成化学株式会社 | Acrylic thermoplastic resin composition and molded article thereof |
-
2006
- 2006-05-26 CN CNA2006800177611A patent/CN101180359A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103380175A (en) * | 2011-02-21 | 2013-10-30 | 株式会社钟化 | Acrylic resin film |
| CN103380175B (en) * | 2011-02-21 | 2015-11-25 | 株式会社钟化 | Acrylic resin film |
| CN103619946A (en) * | 2011-07-01 | 2014-03-05 | 旭化成化学株式会社 | Acrylic thermoplastic resin composition and molded article thereof |
| CN103619946B (en) * | 2011-07-01 | 2016-08-17 | 旭化成株式会社 | Acrylic thermoplastic resin composition and molded body thereof |
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